Process of preparing 1, 1, 2-trichlorethane



Fatented Nov. 24, 1331 when UNETQ STATES? Pihifihl? @FEEQE OTTO ERNST AND HEINRICH LANGE, OF FRANKFORT-ON-THE-MAIN HOCHST, GER- V MANY, ASSIGNORS TO I. G. FABBE'NINDUSTRIE AKTIENGESELISCHAFT, F FRANK- FORT-ON -'1HE-MAI1\T, GERMANY, A CORPORATION OF GERMANY PROCESS OE PREPARING LLE-TMCEORETHANE No Drawing. Application filed September 10, 1928, erial Ho. 805,131, and in Germany September 30, 1927..

Our present invention relates to a process of preparing 1,1,2-trichlorethane.

Several times attempts have been made to prepare trichlorethane, but no process has hitherto been known giving a satisfactory yield. Only the method of Biltz (cf. Berichte der deutschen Chemischen Gesellschaft, volume 35, page 3527) is worth men- I tioning. According to Biltz vinyl chloride is m used as starting material. In order to avoid substitution, vinyl chloride and an insufficient quantity of chlorine is introduced into chloroform at 0 (1, chlorine is then entered until the solution assumes a yellow coloration and the excess of chlorine is subsequently quickly removed by means of caustic soda. After fractionating the product, for several times, trichlorethaneis obtained in a pure state. Experiments have shown that vinyl chloride behaves towards chlorine in an essentially other manner than ethylene. The addition of chlorine takes place much more difficultly than in the case of ethylene, so that the velocity of the substitution as compared with the velocity of the addition is so great as to prevent the formation of trichlorethane 'in a satisfactory yield and purity by simply combining the gases. The above indicated method of working in a solvent at 0 C. is also no suitable way for preparing the trichlorethane in an easy manner on a technical scale. This invention is based on the discovery that a mixture of chlorine gas and vinyl 5 chloride does not essentially change in diffused light, but is almost immediately converted into t-richlorethane without there being an considerable formation of by-products w en exposed to direct sunlight or any 40 suitable artificial source of light. When there is an excess in the gas mixture of about 5 to 10% of vinyl chloride and care is taken that the reaction heat is eliminated by an up propriate arrangement of the apparatus, for as instance a cooling device. pure trichlorcthane can be obtained in a yield of about to per cent of the theory. Superheating of the reaction chamber to over 80 C. should in this case carefully be avoided since from 90 so C. upward substitution again takes place and the gases combine so vigorously that detlagration may occur.

As a result of our research work on the subject we have furthermore found that it is also possible to combine the said two gases in the heat alone without any formation of byproducts, by causing a gas mixture of chlorine and vinyl chloride with an excess of about 5 to 10% of vinyl chloride to react with one another at an elevated temperature, say at be-' tween C. and 250 C. while carefully exeluding all light. The optimum of the temperature is in this case between C. to C. The difference from eth lene is particularly evident from the fact that ethylene reacts with chlorine only at a low temperature without substitution taking place. The trichlorethane can be obtained in a pure state by fractionatin it. The yield amounts to 90 to 95% of the t eory.

Our invention is illustrated, but not limited, by the following exam les:

(1) A mixture of molecu ar quantities of chlorine gas and vinyl chloride containin an excess of vinyl chloride of 10% is passed before a bulb of 150 watts the temperature being kept at between 52 C. and 56 C. Behind the reaction chamber the chlorine has entirely disappeared from the gas residue which roves to be unaltered vinyl chloride. an Thusrom g. of chlorine and 146 g. of the reacting vinyl chloride, 311 g. of the reaction product are obtained from which 284 g. of trichlorethane can be obtained by fractionation. The yield amounts to 91% calculated upon the converted vinyl chloride.

(2) When carrying out the process as indicated in Example 1, there are obtained from 328 g. of chlorine and 289 g. of the reacting vinyl chloride, 614 g. of the reaction product of which 576 g. of trichlorethane are obtained. The yield amounts to 93.5% calculated upon the converted vinyl chloride.

(3) A mixture of molecular quantities of chlorine gas and vin l chloride with an excess of 10% via 1 ch oride is passed at 148 C. to 153 C; .t rough a tube placed in an oven provided with an air bath, light being carefully excluded within the whole apparatus. After the mixture has left the tube, see

he chlorine gas is entirely consumed. From 58 g. of chlorine and 405 g. of the reacting inyl chloride, 839 g. of the crude product ielding 805 g. of trichlorethane are obtained.

The yield amounts to 93% calculated upon be converted vinyl chloride.

We claim:

1. The process of preparing 1,1,2-trihlorethane which consists in causing chloine gas and vinyl chloride to react with one .nother under the influence of light at a temerature of between 0 C. and 80 C. while :xcluding any solvent. v

2. The process of preparing 1,1,2-tri- :hlorethane which consists in causing chlotine gas to act upon gaseous vinyl chloride in lirect light at a temperature of between 0 3. and 80 (3., while excluding any solvent.

3. lhe process of preparing 1,1,2-tri- :hlorethane which consists 1n causing molecular quantities of chlorine gas to act upon molecular quantities of gaseous vinyl :hloridein the presence of an excess of vinyl chloride up to 10% in direct light at a temperature of between 0 C. and 80 (1, while excluding any solvent.

4. The process of preparing 1,1,2-trichlorethane which consists in causing molecular quantities of chlorine gas to act upon molecular quantities of gaseous vinyl chloride in the presence of an excess of vinyl chloride up to 10% in direct sunli ht at a temperature of between 50 C. an 60 C... while excluding any soivent.

In testimony whereof wehave hereunto set our hands.

OTTU ERNST. HMNRICH LANGE. 

